INDICATION OF RELATED APPLICATION
TECHNICAL FIELD
[0002] This invention relates to a ceramic filter used in each of places indicating various
different characteristics and an apparatus for the purification of exhaust gas using
such a filter, and more particularly to a ceramic filter formed by integrally combining
a plurality of filter units having different characteristics, or a ceramic filter
formed by integrally combining a plurality of filter units having different kinds
of catalysts and carrying amounts thereof and an apparatus for the purification for
the purification of exhaust gas using such a filter.
BACKGROUND ART
[0003] Recently, the number of automobiles is exponentially increasing, and an amount of
exhaust gas discharged from an internal engine of the automobile rapidly goes on increasing.
Particularly, various substances including in the exhaust gas discharged from a diesel
engine are a cause raising air pollution and give a serious influence upon natural
environment. Also, there are lately reported study results that particulates in the
exhaust gas (diesel particulate) are a cause raising an allergic obstacle and a reduction
of spermatozoon number, so that it is an urgent issue for humans to take a countermeasure
for removing the particulates in the exhaust gas.
[0004] Under such a situation, there have hitherto been proposed various apparatuses for
the purification of the exhaust gas. As the general apparatus for the purification
of the exhaust gas, there is, for example, a structure that a casing is arranged on
the way of an exhaust pipe connected to an exhaust manifold of an engine and a filter
having fine holes is arranged therein. As a material constituting the filter, there
are metals, alloys and ceramics. As a typical example of the filter made of the ceramic
is well-known a cordierite filter. Recently, porous silicon carbide sintered body
having such merits that the heat resistance, mechanical strength and catching efficiency
are high, and the chemical stability is good, and the pressure loss is low and the
like is used as an example of a filter-forming material.
[0005] The general ceramic filter and the exhaust gas purification apparatus using the same
are such constructed that when the exhaust gas passes through many cells formed along
an axial direction of the filter, fine particles in the exhaust gas are trapped in
the cell walls to remove the fine particles from the exhaust gas. However, a ceramic
filter made of a porous silicon carbide sintered body is generally large in the thermal
expansion and weak to thermal shock, so that there is a problem that as the size becomes
larger, crack is apt to be easily produced. In this connection,
JP-A-8-28246 discloses a ceramic filter being an aggregate formed by combining plural small filter
units as a countermeasure for avoiding the breakage due to cracks. This technique
is a method wherein a honeycomb shaped body of a square pole (honeycomb unit) is formed
by continuously extruding a ceramic raw material through a die of an extrusion shaping
machine and cut into an equal length to form cut pieces, and then the cut pieces are
sintered to form filter units, and a plurality of such filter units are integrally
bundled while adhering outer peripheral faces with each other through a ceramic adhesive
to form an aggregate of these filter units as a ceramic filter.
[0006] Moreover, the ceramic filter is preferable to be wound on its outer peripheral face
with a matt-shaped heat insulating material such as ceramic fibers or the like, and
is received in a casing disposed on the way of an exhaust pipe of an automobile or
the like at such a state.
[0007] In such a filter, as the catching and burning (regeneration) of soot are repeated,
there may be caused the scattering of the catching amount of soot in accordance with
the position of the ceramic filter.
[0008] On the other hand,
JP-A-1-145377 proposes a filter of a honeycomb structure in which an average pore size is stepwise
or continuously increased from a partition wall of a central portion toward a partition
wall of an outer peripheral portion.
[0009] The above conventional technique (
JP-A-1-145377) aims at only the central portion and the outer peripheral portion. In the ceramic
filter having such a structure, when it is arranged in the casing of the exhaust pipe,
there may not be carried out the uniform catching and regeneration. That is, a large
amount of soot is locally and non-uniformly caught on a part of the filter units and
hence the strength as the filter may be lowered in the regeneration or the like. Also,
ash content (ash) included in a fuel additive, engine oil or the like is apt to be
easily stored on a part of the filter units and hence the service life as the filter
may be shortened.
[0010] Also, when the aforementioned conventional ceramic filter is used by repeatedly conducting
the regeneration over a constant period as a whole, as seen from a graph of a regenerating
ratio (a ratio of changing weight before and after the regeneration) shown in FIG.
13, it is confirmed that the soot is surely burnt at an initial stage, but the reactivity
as a catalyst is gradually lowered as the regeneration is repeated several times.
[0011] In the light of the above problems included in the conventional techniques, it is
an object of the invention to provide a ceramic filter in which soot can be equally
caught in axial and radial directions of the filter as a whole and it is effective
to uniformly conduct the regeneration and the high efficiency of removing the exhaust
gas (filter efficiency) can be maintained over a long time and further the durability
is excellent.
[0012] It is another object of the invention to provide an apparatus for the purification
of the exhaust gas using the above ceramic filter having a high filter efficiency
and excellent strength and service life.
DISCLOSURE OF THE INVENTION
[0013] The inventors have made studies for achieving the above objects and confirmed that
the difference in the filter efficiency and the regeneration efficiency is caused
dependent upon an arranging place of the ceramic filter. That is, it is confirmed
that there is a large difference in the flow amount and the flow rate between a near
side and far side of the filter to the exhaust pipe. In general, a casing 8 located
downstream side an exhaust manifold of a diesel engine as an internal combustion engine
is formed so as to make a diameter of its central section larger than those of a first
exhaust pipe and a second exhaust pipe, and the ceramic filter is received in the
casing. In case of such a ceramic filter, the gas flow amount is larger in the filter
located at a position near to a downstream side end portion of the first exhaust pipe
than that in the filter located at a far position (flow rate is faster), and particularly
when the second exhaust pipe is located at an opposite side (lower end side), the
gas flow amount and the flow rate are more increased.
[0014] In this structure, the first exhaust pipe and the second exhaust pipe are connected
so as to position at upstream side and downstream side sandwiching the casing, so
that the flow amount of the central portion of the ceramic filter becomes large (flow
rate is fast) and the flow amount of the peripheral portion thereof is small (flow
rate is slow). As a result, the central portion of the filter is largely affected
by the gas flown thereinto rather than the peripheral portion thereof. In the invention,
therefore, different properties are given to each part in the axial direction of the
ceramic filter (gas flowing direction) or a radial direction perpendicular thereto,
for example, different kinds of filter units dividing into the central portion having
a fast flow rate and the peripheral portion having a slow flow rate are properly combined
to form a ceramic filter, whereby there can be obtained the ceramic filter capable
of conducting uniform catching and regeneration over a whole of the filter. As one
concrete example, it is considered to provide a ceramic filter formed by combining
and bundling plural filter units having different pressure loss property, strength,
length and the like and integrally adhering them.
[0015] The invention is developed under the above idea, and is a ceramic filter having such
a basis construction that different properties are applied to a filter made of porous
ceramic sintered body having a honeycomb structure every part in a gas flowing direction
(axial direction) and/or a radial direction perpendicular thereto.
(A) Particularly, a first embodiment of the invention is a ceramic filter comprising
an aggregate formed by combining a plurality of filter units each made of a columnar,
porous ceramic sintered body having a honeycomb structure and integrally joining them
(so as to bundle in a radial direction), in which said aggregate is constituted by
a combination of two or more kinds of the filter units.
[0016] In the invention, it is preferable to use filter units having different pressure
loss properties as different kinds of the filter unit. As the filter unit having the
different pressure loss property, it is preferable to use a combination of one or
more kinds of either units having different cell wall thicknesses, units having different
porosities, units having different pore sizes and units having different cell structures.
Concretely, a filter unit having a large pressure loss is arranged in a portion having
a fast gas flow rate and a filter unit having a small pressure loss is arranged in
a portion having a slow gas flow rate, and it is preferable to integrally combine
them in the following forms.
① A filter unit having a thick cell wall is arranged in the portion having a fast
gas flow rate, and a filter unit having a thin cell wall is arranged in the portion
having a slow gas flow rate.
② A filter unit having a low porosity is arranged in the portion having a fast gas
flow rate, and a filter unit having a high porosity is arranged in the portion having
a slow gas flow rate.
③ A filter unit having a small pore size is arranged in the portion having a fast
gas flow rate, and a filter unit having a large pore size is arranged in the portion
having a slow gas flow rate.
④ A filter unit having a large cell density is arranged in the portion having a fast
gas flow rate, and a filter unit having a small cell density is arranged in the portion
having a slow gas flow rate.
[0017] In the invention, as an example of different kinds of the filter units can be used
filter units having different strengths. It is preferable that a filter unit having
a high strength is arranged in the portion having the fast gas flow rate and a filter
unit having a low strength is arranged in the portion having a slow gas flow rate,
but a case reverse thereto may be conducted.
[0018] As an example of the different kinds of the filter units in the invention, filter
units having different lengths can be used.
[0019] According to the invention of the above construction, when a plurality of at least
two kinds of columnar filter units are combined in a direction perpendicular to an
axial direction at a bundle state, the combination can be properly changed in accordance
with the situation of exhaust gas flown into the ceramic filter as compared with a
wholly uniform monolith-type ceramic filter or a ceramic filter consisting of a combination
of the same kind of filter units, and hence it is possible to conduct the uniform
catching and regeneration without causing displacement at positions of the ceramic
filter. Particularly, by combining filter units having different properties, materials
or the like in the axial direction or radial direction of the filter, the physical
properties such as thermal conductivity and the like can be changed in accordance
with the places of the filters and hence the uniform catching and regeneration of
the ceramic filter as a whole can be ensured.
[0020] For example, by combining a filter unit having a high pressure loss with a filter
unit having a low pressure loss can be easily flown the exhaust gas into the filter
unit having the low pressure loss. Therefore, the aggregate as the ceramic filter
can be more effectively manufactured by arranging the filter unit having a low pressure
loss in places having a small flow amount of the exhaust gas.
[0021] Under the same keystone as mentioned above, ① the exhaust gas in the ceramic filter
can be guided toward a position of low pressure loss by integrally combining a filter
unit(s) having a high pressure loss located at a portion having a relatively fast
flow rate and a filter unit(s) having a low pressure loss located at a portion having
a relatively slow flow rate; ② a filter unit(s) being thin in the wall thickness and
easy in the pass of the gas is arranged in place(s) having a small flow amount of
the exhaust gas; ③ a filter unit(s) having a thick wall thickness is arranged in a
portion having a fast gas flow rate, while a filter unit(s) having a thin wall thickness
is arranged in a portion having a slow flow rate, whereby the exhaust gas in the ceramic
filter can be guided toward place having a low pressure loss; ④ a filter unit(s) having
a high porosity is arranged in place having a small flow amount of the exhaust gas;
⑤ a filter unit(s) having a low porosity is arranged in a portion having a fast flow
rate, while a filter unit(s) having a high porosity is arranged in a portion having
a slow flow rate, whereby the exhaust gas in the ceramic filter can be guided toward
place having a low pressure loss; and ⑥ the filter unit having a large pore size is
low in the pressure loss during and after the catching as compared with the filter
unit having a small pore size and hence it is effective to arrange the filter unit
having a large pore size in place having a small flow amount of the exhaust gas. That
is, when a fluid is passed through the ceramic filter, the exhaust gas in the ceramic
filter can be guided toward a place having a low pressure loss by combinedly arranging
the filter unit having a small pore size in a portion having a relatively fast flow
rate and the filter unit having a large pore size in a portion having a relatively
slow flow rate.
[0022] In the above construction of the invention, as the filtering area of the ceramic
filter is made large by fining the cell structure of the filter unit, the pressure
loss in and after the catching becomes low. Therefore, the uniform catching can be
effectively conducted by arranging the filter unit having a high cell density in a
portion having a low flow amount of the exhaust gas.
[0023] When the fluid is passed through the above ceramic filter, the filter unit having
a large cell density is arranged in the portion having a relatively fast flow rate
and the filter unit having a small cell density is arranged in the portion having
a relatively slow flow rate, whereby the exhaust gas in the ceramic filter can be
guided toward a place in the ceramic filter having a low pressure loss of the exhaust
gas.
[0024] According to the invention, there can be used filter units having different strengths.
That is, a filter unit having a high strength is used in a portion of the ceramic
filter subjected to thermal shock, whereby the strength as the aggregate of the ceramic
filter can be improved.
[0025] During the studies for achieving the above object, the inventors have further made
various experiments for solving the cause of the deterioration of the filter performance.
For example, there is made a test for increasing a catalyst carrying amount of the
filter. In this case, however, the pressure loss of the filter becomes higher and
the progress of the deterioration can not be prevented. Then, temperatures at plural
places are measured by inserting a thermocouple into the filter to be regenerated.
Contrary to expectation, it has been confirmed that a temperature difference is caused
in positions of the filter, for example, between the central portion and outer peripheral
portion. That is, the temperature of the filter in the central portion is higher than
that of the filter in the outer peripheral portion.
[0026] Now, the temperature is measured by changing a connecting relationship between the
filter and the casing as shown in FIG. 12. As a result, the temperature distribution
appearing in the filter differs in accordance with the difference in the connecting
position between the exhaust pipe and the casing as shown in FIG. 12, and particularly
the filter temperature tends to become high in the portion near to the exhaust pipe.
Therefore, when conducting the temperature control of the filter, if it is intended
to control the temperature to about 600°C well promoting the reaction of the catalyst,
it is confirmed that a portion rendering into a high temperature exceeds 800°C. Also,
as the construction of the catalyst itself is examined, it is confirmed that a noble
metal used as the catalyst causes sintering (metal changes into large particles) immediately
above 800°C and the reactivity becomes bad and the use thereof is impossible.
[0027] From these facts, the inventors have knowledge that when the ceramic filter is constituted
with an aggregate of columnar filter units dividable in a radial direction as mentioned
above, it is effective to carry different catalysts on the respective columnar filter
units or change a carrying amount of the catalyst on the filter unit.
[0028] (B) That is, a second embodiment of the invention is a ceramic filter comprising
an aggregate formed by combining a plurality of columnar filter units each having
a honeycomb structure and made of porous ceramic sintered body through a sealing material
layer (preferably a sealing material indicating an adhesiveness: adhesive layer) and
integrally joining them, in which the aggregate is constituted by combining two or
more kinds of the filter units and a catalyst of different carrying amount or different
kind is carried on each of the filter units.
[0029] In this embodiment, as the different kinds of the filter units carrying the catalyst
of different carrying amount or different kind can be used one or more of the filter
units having different pressure loss properties, the filter units having different
strengths and the filter units having different lengths as mentioned above.
[0030] As the filter units having different pressure loss properties can be used one or
more of units having different thicknesses of cell wall, units having different porosities,
units having different pore sizes and units having different cell structures.
[0031] In the invention, catalysts having different heat resistance or catalytic activities
can be used as the different kinds of the catalyst.
[0032] As the applying embodiment of the invention, it is preferable that when a high-temperature
gas is flown in the ceramic filter, a filter unit carried with a catalyst having a
good heat resistance is arranged in a portion having a fast gas flow rate or a large
gas flow amount and/or a filter unit carried with a catalyst having a poor heat resistance
is arranged in a portion having a slow gas flow rate or a small gas flow amount and
they are integrally combined to form a ceramic filter.
[0033] Alternatively, it is preferable that when a high-temperature gas is flown in the
ceramic filter, a filter unit carried with a catalyst having a large activity is arranged
in a portion having a fast gas flow rate or a large gas flow amount and/or a filter
unit carried with a catalyst having a small activity is arranged in a portion having
a slow gas flow rate or a small gas flow amount.
[0034] In the invention, it is further preferable to combine a plurality of filter units
having different carrying amounts of the catalyst and integrally join them.
[0035] Furthermore, in the invention, it is preferable that when the ceramic filter is set
in a casing of an exhaust gas purifying apparatus and a high-temperature gas is flown
therein, a filter unit having a small carrying amount of a catalyst is arranged in
a portion having a fast gas flow rate or a large gas flow amount and/or a filter unit
having a large carrying amount of a catalyst is arranged in a portion having a slow
gas flow rate or a small gas flow amount.
[0036] In the invention, the ceramic filter may be an aggregate formed by integrally joining
a plurality of filter units each made of columnar and porous ceramic sintered body
having a honeycomb structure through a sealing material layer, in which the aggregate
is constituted with a combination of two or more different kinds of the filter units
and the filter units are an integral combination of a unit not carrying the catalyst
and a unit carrying at least one kind of catalysts.
[0037] In the invention, it is particularly preferable that when the high-temperature gas
is flown in the ceramic filter, the filter unit carrying the catalyst is arranged
in a portion having a slow gas flow rate or a small flow amount.
[0038] The invention having the above construction has the function and effect as mentioned
below. That is, in the invention, all of the filter unit fundamentally combined as
the ceramic filter do not carry the same catalyst, but the different catalyst is carried
every the filter unit, so that there can be provided a ceramic filter suitable for
an exhaust gas purifying apparatus of an automobile causing a deflected gas flowing.
[0039] For example, an example of arranging catalysts having different heat resistances
in accordance with positions in the radial direction of the filter or an example of
carrying catalysts having different catalytic activities means that the catalyst most
suitable in the use of the ceramic filter is selectively attached to the respective
position.
[0040] Particularly, when the ceramic filter is set in the casing of the exhaust gas purifying
apparatus and the high-temperature exhaust gas is flown thereinto, the filter carried
with the catalyst having an excellent heat resistance is used in a portion having
a fast flow rate or a large gas flow amount of the exhaust gas, whereby the catalyst
in a position exposed to the high-temperature portion can be used over a long time.
[0041] Similarly, when the high-temperature gas is flown into the ceramic filter, the regeneration
can be efficiently conducted even in a portion of a relatively low temperature by
using the filter carried with the catalyst having a large activity in the portion
having a slow gas flow rate or a small gas flow amount.
[0042] Also, in the invention, the carrying amount of the catalyst may be changed in accordance
with the place in the radial direction of the filter (the same catalyst amount may
not be carried on the filter). In this case, it is possible to adjust the catalyst
weight or density to be carried on the filter in the use of the ceramic filter. According
to such a structure, it is not necessary to carry the same catalyst amount on the
ceramic filter. In the use of the ceramic filter, therefore, it is possible to arrange
the filter unit having catalyst weight and density adjusted to a large level in a
portion having a relatively low temperature and arrange the filter unit having catalyst
weight and density adjusted to a small level in a portion having reversely a relatively
high temperature.
[0043] Further, according to the invention, the aggregate of the ceramic filter can be formed
by using both a filter unit carried with the catalyst and a filter unit not carried
with the catalyst. Thus, the filter unit having no catalyst can be used in a portion
promoting the regeneration of soot without the catalyst at a relatively high temperature,
while the filter unit having the catalyst can be used in a portion requiring the catalyst
effect at a relatively low temperature.
[0044] In this case, it is possible to arrange the filter unit having the catalyst in a
portion having a small flow amount of the exhaust gas and being relatively low in
the temperature and reversely arrange the filter unit having no catalyst in a portion
having a large flow amount of the exhaust gas and being relatively high in the temperature
in the use of the ceramic filter.
[0045] According to the invention, the ceramic filter having the above properties can be
interposed between the first and second exhaust pipes to form an exhaust gas purifying
apparatus having a high strength and capable of using over a long time.
[0046] Furthermore, according to the invention, when the fluid is passed through the ceramic
filter, a filter unit having a high strength arranged in a portion having a relatively
fast flow rate and a filter unit having a low strength arranged in a portion having
a relatively slow flow rate are integrally combined, whereby there can be provided
a ceramic filter capable of coping with the rapid temperature change of the exhaust
gas.
[0047] In addition, according to the invention, when the fluid is passed through the ceramic
filter, a filter unit having a low strength arranged in a portion having a relatively
fast flow rate and a filter unit having a high strength arranged in a portion having
a relatively slow flow rate are integrally combined, whereby there can be provided
a ceramic filter capable of coping with the temperature change generated when abnormal
burning is caused due to unburnt soot in the portion having the slow flow rate. These
ceramic filters-can be properly selected and used in accordance with the specification
of the engine and the regeneration system.
[0048] Further, according to the invention, the ceramic filter may be formed by changing
a filter length and arranging a filter unit having a short length in a portion having
a small catching amount of soot. In the ceramic filter having such a construction,
the position of soot amount from front edge face can be made same. As a result, the
aggregate of the filters can promote the catching of soot and regeneration as whole.
[0049] Moreover, in the invention, a ceramic filter having a high filtering efficiency,
a low pressure loss and excellent heat resistance and thermal conductivity can be
provided by using a porous silicon carbide sintered body as a material for the ceramic
filter.
[0050] (C) As a third embodiment of the invention, there is proposed an exhaust gas purifying
apparatus having a high strength and capable of using over a long time by interposing
and arranging various ceramic filters having different properties in an axial direction
and/or a radial direction in a casing between first and second exhaust pipes.
BRIEF DESCRIPTION OF DRAWINGS
[0051]
FIG. 1 is a schematic view illustrating an example of the exhaust gas purifying apparatus.
FIG. 2 is a perspective view of a block formed by combining filter units.
FIG. 3 is an enlarged section view of a main part of an exhaust gas purifying apparatus.
FIG. 4 is an explanatory view of a pressure loss property.
FIG. 5 is a graph showing results of Reference Example indicating a difference of
soot catching amount in accordance with a difference of arranging positions of a casing
and an exhaust pipe.
FIG. 6 is a graph showing results of Comparative example indicating a difference of
soot storing amount by changing a shape of a filter.
FIG. 7 is a graph showing results of Comparative Example indicating a difference of
soot storing amount by changing a length of a filter.
FIG. 8 is a view showing an example of carrying alumina on a ceramic filter of an
embodiment of the invention.
FIG. 9 is a graph showing a relation between specific surface area exerting upon a
heat resistance of a catalyst and a heat treating time.
FIG. 10 is a graph showing a relation between a regeneration ratio and a temperature
exerting upon an activating temperature of a catalyst.
FIG. 11 is a schematically section view of an example of carrying a catalyst.
FIG. 12 is a section view illustrating a way of temperature propagation by changing
arranging places of a casing and an exhaust pipe.
FIG. 13 is a graph showing a regeneration ratio after the use several times.
BEST MODE FOR CARRYING OUT THE INVENTION
[0052] An exhaust gas purifying apparatus 1 for a diesel engine as an embodiment of the
invention and a ceramic filter used therefor are explained with reference to FIG.
1 to FIG. 13 below.
[0053] The exhaust gas purifying apparatus 1 shown in FIG. 1 is an apparatus for purifying
an exhaust gas discharged from a diesel engine 2 as an internal combustion engine.
The diesel engine 2 comprises plural cylinders not shown, and each cylinder is connected
to a branched part 4 of an exhaust manifold 3 made of a metallic material. Each branched
part 4 is joined to a main body 5 of the manifold. Therefore, exhaust gas discharged
from the each cylinder is collected to the manifold main body.
[0054] To a downstream side of the exhaust manifold 3 are arranged a first exhaust pipe
6 and a second exhaust pipe 7 each made of a metallic material. An end portion of
an upstream side of the first exhaust pipe 6 is connected to the manifold main body
5, and a cylindrical casing 8 made of a metallic material is arranged between the
first exhaust pipe 6 and the second exhaust pipe 7. That is, an end portion of an
upstream side of the casing 8 is connected to an end portion of a downstream side
of the first exhaust pipe 6, and an end portion of a downstream side of the casing
8 is connected to an end portion of an upstream side of the second exhaust pipe 7.
In other words, the casing 8 is arranged at an interposing state between the exhaust
pipes 6, 7. As a result, internal regions of the first exhaust pipe 6, casing 8 and
second exhaust pipe 7 are communicated with each other and an exhaust gas is flown
thereinto. A section at a central portion of the casing 8 is made larger than diameters
of the exhaust pipes 6, 7, so that the internal region of the casing 8 is wider than
the internal regions of the exhaust pipes 6, 7. In the casing 8 is received a ceramic
filter 9.
[0055] A heat insulating material 10 is interposed between an outer peripheral face of the
ceramic filter 9 and an inner peripheral face of the casing 8. The heat insulating
material 10 is a matt containing ceramic fibers and has a thickness of 2 mm - 60 mm.
It is desirable that the heat insulating material 10 has an elastic structure and
a function of releasing heat stress. The heat insulating material prevents the escape
of heat from the outermost peripheral portion of the filter 9, whereby energy loss
in the regeneration can be suppressed to a minimum, and also since it has the elastic
structure, the shifting of the position of the ceramic filter 9 due to the pressure
of the exhaust gas and the vibration during the running can be prevented.
[0056] In this embodiment, a main application of the ceramic filter 9 is a diesel particulate
filter (DPF) for removing diesel particulates in the exhaust gas discharged from the
diesel engine. A block 9 constituting the filter shown in FIG. 2 is formed by bundling
a plurality of ceramic filter units F1 having a honeycomb structure so as to combine
faces perpendicular to an axial direction with each other and integrally uniting them
to form an aggregate (block). A filter unit F1 positioned in a central portion of
the aggregate is quadratic prism-shaped, an outer size of which is 33 mm x 33 mm x
150 mm. In the illustrated embodiment, quadratic prism-shaped filter units F1 are
bundled in 4 rows and 4 columns, i.e. a total of 16 units to form a quadratic prism-shaped
aggregate (ceramic filter) of honeycomb filter units as a whole.
[0057] These filter units F1 are preferable to be made of a porous silicon carbide sintered
body. Because, the silicon carbide sintered body is excellent in the heat resistance
and thermal conductivity as compared with the other ceramics. Of course, sintered
bodies of silicon nitride, sialon, alumina, cordierite, mullite and the like can be
used as a sintered body other than silicon carbide. Further, as the unit F1 can be
used a silicon-containing ceramic formed by compounding metallic silicon with the
above ceramic, or a ceramic bonded with silicon or a silicate compound.
[0058] Also, each of these filter units F1 is provided with a honeycomb structure, so that
there is an advantage that even when the catching amount of particulates increases,
the pressure loss is small. In each of the filter units F1 are regularly formed plural
through-holes 12 having substantially a quadrate at section along an axial direction
of the unit. The through-holes 12 are partitioned with each other through thin cell
walls 13, and an oxidation catalyst consisting of an element of platinum group (e.g.
Pt or the like) or the other metal element or an oxide thereof is carried on the cell
wall 13. Of course, a catalyst purifying Ca, HC, Nox or the like may be carried, or
a rare earth element, alkaline earth metal, alkali metal, transition metal may be
carried.
[0059] As shown in FIG. 13, opening portions of each through-hole 12 are sealed with a plug
14 (porous silicon carbide sintered body in this embodiment) at either one of end
faces 9a, 9b, and viewing the whole of the end faces 9a, 9b, the opening portions
and the sealed portions are constructed so as to indicate a checkered pattern.
[0060] As a result, the filter unit F1 is at a state of constituting with many cells having
a quadratic form at section. In such a cell structure, a density of the cells is about
100-400 cells/inch square and a thickness of the cell wall 13 is about 0.05-0.5 mm.
[0061] Moreover, the cell structure is generally represented by dividing the thickness of
the cell wall 13 as a unit of mil (1 mil is 0.0254 mm) by the cell density. That is,
the above example is represented by 14/200. Therefore, about a half of many cells
are opened at the upstream side end faces 9a, and the remaining half are opened at
the downstream side end faces 9b.
[0062] In the filter unit F1, the average pore size is 1 µm - 50 µm, preferably about 5
µm - 20 µm. When the average pore size is less than 1 µm, the clogging of the filter
unit F1 due to the deposition of the particulates becomes conspicuous. While, when
the average pore size exceeds 50 µm, fine particulates can not be caught and the filtering
ability lowers.
[0063] The porosity of the filter unit F1 is 30% - 80%, preferably 35% - 70%. When the porosity
is less than 30%, the unit becomes too dense and there is a fear that the exhaust
gas can not be flown into the interior of the unit. While, when the porosity exceeds
80%, the pores in the filter unit F1 becomes too large and there is a fear that the
strength becomes weak and the catching efficiency of the particulates lowers.
[0064] In the ceramic filter 9 placed in the casing as shown in FIG. 3, outer peripheral
faces of 16 ceramic filters 9 in total are adhered with each other through ceramic
sealing materials (preferably using an adhesion sealing material (adhesive)) 15. The
sealing material layer 15 is preferable to have a thickness of about 0.3 mm - 3 mm,
further preferably 0.5 mm - 2 mm. When the thickness is exceeds 3 mm, even if the
thermal conductivity is high, the sealing material layer 15 is still a large heat
resistor and hence the thermal conduction between the filter units F1 is obstructed.
Also, a ratio of the filter unit F1 portion occupied in the ceramic filter 9 is relatively
decreased to bring about the lowering of the filtering ability. Inversely, when the
thickness of the sealing material layer 15 is less than 0.3 mm, the large heat resistor
is not formed, but the adhesion property between the filter units F1 is lacking and
the ceramic filter 9 is easily broken.
[0065] The sealing material layer 15 is made of, for example, inorganic fibers, an inorganic
binder, an organic binder and inorganic particles, and is desirable to be made of
an elastic material formed by binding three-dimensionally crossed inorganic fibers
and inorganic particles through the inorganic binder and organic binder. As the inorganic
fiber may be used one or more ceramic fibers selected from silica-alumina fibers,
mullite fibers, alumina fibers and silica fibers. Among them, the use of the silica-alumina
ceramic fibers is desirable. Because, the silica-alumina ceramic fiber is excellent
in the elasticity and has an action of absorbing heat stress.
[0066] In this case, the content of the silica-alumina ceramic fibers occupied in the sealing
material layer 15 is 10% by weight - 70% by weight, preferably 10% by weight - 40%
by weight, more preferably 20% by weight - 30% by weight as a solid content. When
the content is less than 10% by weight, the function and effect as the elastic body
lower. While, when the content exceeds 70% by weight, not only the thermal conductivity
but also the elasticity lower.
[0067] The silica-alumina ceramic fiber is preferable to contain shots of 1% by weight -
10% by weight, preferably 1% by weight - 5% by weight, more preferably 1% by weight
- 3% by weight. When the shot content is less than 1% by weight, the production is
difficult, while when it exceeds 50% by weight, The outer peripheral face of the filter
unit F1 is damaged.
[0068] The silica-alumina ceramic fiber has a fiber length of 1 mm - 100 mm, preferably
1 mm - 50 mm, more preferably 1 mm - 20 mm. When the fiber length is less than 1 mm,
the elastic structural body can not be formed, while when the fiber length exceeds
100 mm, the fibers are pilled and the dispersibility of the inorganic particles is
deteriorated, and further it is difficult to thin the sealing material layer 15 to
not more than 3 mm and hence it is not attempted to improve the thermal conduction
between the filter units F1.
[0069] As the inorganic binder included in the sealing material layer 15 is desirable at
least one colloidal sol selected from silica sol and alumina sol. Particularly, it
is desirable to select the silica sol. Because, the silica sol is available and easily
changes into SiO
2 through firing and is suitable as an adhesive at a high temperature region. Also,
the silica sol is excellent in the insulating property.
[0070] Furthermore, the content of the silica sol in the sealing material layer 15 is 1%
by weight - 30% by weight, preferably 1% by weight - 15% by weight, more preferably
5% by weight - 9% by weight as a solid content. When the content is less than 1% by
weight, the adhesion strength lowers, while when the content exceeds 30% by weight,
the thermal conductivity largely lowers.
[0071] As the organic binder contained in the sealing material layer 15, a hydrophilic organic
high polymer is preferable, and at least one polysaccharide selected from polyvinyl
alcohol, methylcellulose, ethylcellulose and carboxymethyl cellulose is more preferable.
Among them, it is desirable to select carboxymethyl cellulose. Because, carboxymethyl
cellulose gives a preferable fluidity to the sealing material layer and indicates
an excellent adhesiveness at a room temperature region. In this case, the content
of the carboxymethyl cellulose in the adhesive layer is 0.1% by weight - 5.0% by weight,
preferably 0.2% by weight - 1.0% by weight, more preferably 0.4% by weight - 0.6%
by weight as a solid content. When the content is less than 0.1% by weight, migration
can not be sufficiently controlled.
[0072] Moreover, the term "migration" used herein means a phenomenon that in case of curing
the sealing material layer filled between bodies to be adhered, the binder moves accompanied
with the removal of the solvent through drying. While, when the content exceeds 5.0%
by weight, the organic binder burns out at a higher temperature and the strength of
the sealing material layer 15 lowers.
[0073] As the inorganic particles included in the sealing material layer 15 is preferable
an elastic material using one or more inorganic powder or whisker selected from silicon
carbide, silicon nitride and boron nitride. Such carbide and nitride are very large
in the thermal conductivity and contribute to improve the thermal conduction owing
to the inclusion on a surface of the ceramic fiber or a surface of the colloidal sol
and interiors thereof. Among the inorganic powder of the carbide and nitride, it is
desirable to select silicon carbide powder. Because, silicon carbide is very high
in the thermal conductivity and has a property of being easily familiar with the ceramic
fiber. Further, the filter unit F1 as a body to be adhered is the same kind, i.e.
porous silicon carbide in this embodiment.
[0074] In this case, the content of silicon carbide powder is 3% by weight - 80% by weight,
preferably 10% by weight - 60% by weight, more preferably 20% by weight - 40% by weight
as a solid content. When the content is less than 3% by weight, the thermal conductivity
of the sealing material layer 15 lowers and hence the sealing material layer 15 becomes
still a large heat resistor. While, when the content exceeds 80% by weight, the adhesion
strength at high temperatures lowers.
[0075] In the silicon carbide powder, the particle size is 0.01 µm - 100 µm, preferably
0.1 µm - 15 µm, more preferably 0.1 µm - 10 µm. When the particle size exceeds 100
µm, the adhesion force and thermal conductivity lower, while when the particle size
is less than 0.01 µm, the cost of the sealing material layer 15 increases.
[0076] The production method of the above ceramic filter is described below.
① At first, there are previously provided a ceramic starting slurry used in an extrusion
shaping step, a plug paste used in an end face sealing step, and a sealing material
paste used in a filter adhering step. The ceramic starting paste is used by compounding
given amounts of an organic binder and water with silicon carbide powder and mixing
them. The plug paste is used by compounding an organic binder, a lubricant, a plasticizer
and water with silicon carbide powder and mixing them. The paste for the formation
of the sealing material layer is used by compounding given amounts of inorganic fibers,
an inorganic binder, an organic binder, inorganic particles and water and mixing them.
② Then, the ceramic starting slurry is charged into an extrusion shaping machine and
continuously extruded into a mold. Thereafter, the extruded honeycomb shaped body
is cut at an equal length to obtain cut pieces of a quadratic, columnar honeycomb
shaped body. Thereafter, a given amount of the plug paste is filled in one-sided opening
portion of a cell of the cut piece to seal both end faces of each of the cut pieces.
③ Next, the firing is carried out under given conditions of temperature, time and
the like to completely sinter the cut pieces of the honeycomb shaped body and the
plug 14. Moreover, in order to provide an average pore size of 6 µm - 15 µm and a
porosity of 35% - 70%, the firing temperature is set to 2100°C - 2300°C and the firing
time is set to 0.1 hour - 5 hours, and an atmosphere inside a furnace in the firing
is an inert atmosphere and a pressure of the atmosphere is an ordinary pressure.
④ If necessary, an underground layer made of a ceramic is formed on an outer peripheral
face of the honeycomb filter unit F1, and thereafter the paste for the formation of
the sealing material layer is applied thereonto. The thus obtained filter unit F1
is used in total of 16 units and their outer peripheral faces are adhered with each
other to form a columnar aggregate as an objective ceramic filter. Of course, the
ceramic filter may be subjected to a working into a target shape such as column, ellipsoid
or the like and coated with a sealing material.
[0077] Next, an action of catching particulates through the ceramic filter 9 received in
the casing 8 will be described. In the ceramic filter 9, the exhaust gas is fed from
a side of the upstream side end face 9a. That is, the exhaust gas flown from the first
exhaust pipe 6 first flows into the cell opening to the upstream side end face 9a
of the ceramic filter. Then, the exhaust gas passes through the cell wall 13 and flows
into the adjoining other cell (i.e. adjoining cell at a side opening to the downstream
side end face 9b), which is discharged from the opening downstream side end face 9b.
In such a flowing of the gas, particulates included in the exhaust gas (diesel particulate)
can not pass through the cell wall 13, so that they are trapped on the surface of
the cell wall 13 as they are. As a result, the purified exhaust gas is discharged
from the downstream side end face 9b of each filter unit F1. Then, the purified exhaust
gas passes through the second exhaust pipe 7 and is finally discharged into air.
[0078] Moreover, the particulates trapped by the cell wall 13 are burnt out by the action
of the catalyst when the internal temperature of the ceramic filter 9 reaches to a
given temperature.
[0079] Then, the ceramic filter (A) according to the invention is described with respect
to an example of the aggregate formed by combining filter units F1 having different
properties in the radial direction of the filter, e.g. different pressure loss properties,
but the invention is not limited to this example.
[0080] In general, the pressure loss property when the exhaust gas passes through the cell
wall 13 is considered as follows. The pressure loss when the diesel exhaust gas passes
through the filter unit F1 can be shown in FIG. 4. In this case, resistances ΔP1,
ΔP2 and ΔP3 are values dependent upon the cell structure of the filter unit F1, respectively,
and a total value of Δpi = (ΔP1 + ΔP2 + ΔP3) is a constant value not dependent upon
the deposited amount and time of the diesel particulates, which is called as an initial
pressure loss. On the other hand, ΔP4 is a resistance when the diesel particulates
pass through the cell wall 13 of the filter unit F1 after the deposition, which is
a value corresponding to 2-3 times or more of the initial pressure loss.
① When the cell wall 13 is thickened, the resistance ΔP3 passing through the cell
wall 13 increases as the pressure loss. Further, the opening becomes small and hence
ΔP1 becomes large. As a result, the pressure loss becomes considerably large as compared
with the filter having a thin cell wall 13, and the tendency thereof becomes more
conspicuous when the particulates are deposited on the filter.
② In case of increasing the porosity, the resistance ΔP3 passing through the cell
wall 3 lowers as the pressure loss. Therefore, the pressure loss becomes small as
compared with the filter having a low porosity, and the tendency thereof becomes more
conspicuous when the particulates are deposited on the filter.
③ In case of increasing the pore size, the resistance ΔP3 passing through the cell
wall 13 lowers as the pressure loss. Therefore, the pressure loss becomes small as
compared with the filter having a low pore size, and the tendency thereof becomes
more conspicuous when the particulates are deposited on the filter.
④ In case of making the cell density large, the resistance ΔP1 based on the narrowing
of the opening in each cell path and the resistance ΔP2 passing through the fine pipe
increases as the pressure loss. However, the resistance ΔP4 in case of passing the
deposited soot considerably lowers, so that the pressure loss becomes small as compared
with the filter having a low cell density.
[0081] In the invention, therefore, it is considered to combine different kinds of filter
units F1 (cell wall thickness, porosity, pore size, cell structure) in accordance
with loss property of each filter unit F1 constituting the ceramic filter 9. For example,
the filter unit F1 having a large pressure loss is arranged in a portion having a
fast gas flow rate and the filter unit F1 having a small pressure loss is arranged
in a portion having a slow gas flow rate, and they are integrally combined. Concrete
examples thereof are mentioned as follows.
① A filter unit having a thick cell wall is arranged in the portion having a fast
gas flow rate, and a filter unit having a thin cell wall is arranged in the portion
having a slow gas flow rate.
② A filter having a low porosity is arranged in the portion having a fast gas flow
rate, and a filter unit having a high porosity is arranged in the portion having a
slow gas flow rate.
③ A filter unit having a small pore size is arranged in the portion having a fast
gas flow rate, and a filter unit having a large pore size is arranged in the portion
having a slow gas flow rate.
④ A filter unit having a large cell density is arranged in the portion having a fast
gas flow rate, and a filter unit having a small cell density is arranged in the portion
having a slow gas flow rate.
[0082] Also, in the invention, filter units having different strengths can be used as an
example of different kinds of filter units F1. In this case, a filter unit having
a high strength is arranged in the portion having a fast gas flow rate and a filter
unit having a low strength is arranged in the portion having a slow gas flow rate
in accordance with the specification of the engine and the regeneration system, or
the arrangement of these filter units is opposite, so that the combination thereof
can be properly selected.
[0083] Furthermore, in the invention, honeycomb filters having different lengths can be
used as an example of different kinds of the filter units F1.
[0084] Then, the ceramic filter (B) according to the invention is described with respect
to an example of the aggregate formed by combining filter units F1 having different
kinds of catalyst carried on the filter unit F1 and/or different carrying amounts,
but the invention is not limited to this example. The catalyst formed on the each
filter unit F1 is described below.
[0085] The catalyst used in the invention (B) is preferable to be a rare earth oxide-containing
alumina film 17 separately coating the surface of each SiC particle 16 with respect
to SiC particles 16 of SiC sintered body constituting the cell walls 13 partitioning
each cell of the filter unit F1.
[0086] In general, alumina has a high specific surface area and is suitable as a catalyst
carrying film. Particularly, it is desirable to develop filter units F1 stably acting
at a higher temperature and having a high heat resistance at the present time, and
the alumina film 17 is required to have a higher heat resistance accompanied therewith.
[0087] In the invention, in order to improve the alumina film, ① the shape of each alumina
particle is rendered into a small fiber and ② a rare earth oxide such as ceria (cerium
oxide) or the like is included therein. Particularly, by adopting the structure of
the former ① can be reduced contact points between alumina particles and the sintering
rate can be lowered to suppress the growth of particles and make the specific surface
area large to thereby improve the heat resistance. That is, in this embodiment, the
alumina film 17 covering the surface of each SiC particle in the filter unit F1 shows
a hair implant structure that alumina particles stand up in form of small fibers at
a microscopic section. In such a filter unit F1, therefore, the heat resistance is
considerably improved because the contact points between adjoining alumina small fibers
is reduced. In the latter ②, the heat resistance is improved by adding ceria or the
like. This is due to the fact that a new compound is formed on the surfaces of the
crystal particles constituting the alumina film 17 to obstruct the growth of alumina
particles.
[0088] In this embodiment, SiC or SiO
2 existing on an extreme surface layer thereof feeds Si in the heat treatment to shut
off a mass transfer course, whereby the heat resistance is improved. According to
the inventors' studies, it is confirmed that when SiC is intentionally treated at
a high temperature to form an oxide, the heat resistance is further improved.
[0089] The regeneration property of the alumina film 17 is described below. The alumina
film 17 is obtained by adding a rare earth oxide such as ceria (CeO
2) or lanthana (La
2O
3) in an amount of about 10-80 mass%, preferably 20-40 mass% based on Al
2O3 and uniformly dispersing the oxide into the surface or interior of the alumina
film 17. As ceria or the like is added to the alumina film 17 (it is desirable to
add a catalyst such as Pt or the like together), the feeding of oxygen into the exhaust
gas is activated by an action of adjusting oxygen concentration inherent to ceria,
whereby the efficiency of burning and removing "soot (diesel particulates) adhered
to the filter unit F1 is improved and hence the regeneration ratio of the filter unit
F1 is considerably improved. Also, the durability of the filter unit F1 can be improved.
[0090] That is, the rare earth oxide such as ceria or the like improves the heat resistance
of alumina but also plays a role of adjusting the oxygen concentration on the surface
of the filter unit F1. In general, hydrocarbon or carbon monooxide existing in the
exhaust gas is removed by oxidation reaction and NOx is removed by reducing reaction.
Ceria added to the catalyst is relatively low in the redox potential of Ce
3+ and Ce
4+ and reversibly promotes a reaction of 2CeO
2 ↔ Ce
2O
3 + 1/2O
2. That is, when the exhaust gas renders into a rich region, the above reaction proceeds
to the right to feed oxygen into an atmosphere, while when it renders into a lean
region, the reaction proceeds to the left to occlude extra oxygen in the atmosphere.
Thus, the ceria adjusts the oxygen concentration in the atmosphere and takes an action
of widening a width of an air-fuel ratio so as to efficiently remove hydrocarbon,
carbon monooxide or NOx.
[0091] On the contrary, the catalyst containing no CeO
2 oxidizes soot by activating oxygen in the exhaust gas. This reaction is poor in the
efficiency because oxygen in the fluid should be activated.
[0092] On the other hand, the catalyst containing CeO
2 feeds oxygen by the following reaction formula:
CeO
2 ↔ CeO
2-x + ×/2O
2
That is, oxygen discharged into the atmosphere and oxygen in the exhaust gas are activated
by the catalyst (noble metal) and reacted with soot (carbon) to form CO
2 (CeO
2-x is oxidized to original CeO
2). Also, CeO
2 and soot directly contact with each other, so that even if the oxygen amount discharged
is small, the soot can be efficiently oxidized.
[0093] Further, CeO
2 increases OSC (oxygen storing capacity) owing to the carrying of the catalyst (noble
metal). Because, the catalyst (noble metal) activates oxygen in the exhaust gas and
activates oxygen on the surface of CeO
2 near to noble metal, and the OSC is increased.
[0094] Moreover, as the rare earth oxide, it is preferable to use a composite oxide of rare
earth element and zirconium in addition to the above single oxide (CeO
2). In this case, it is considered that when zirconium oxide is included in the rare
earth oxide, the grain growth of the rare earth oxide is suppressed to improve the
controlling property of oxygen concentration.
[0095] In the rare earth oxide forming a composite oxide with zirconium, the particle size
is preferably about 1-30 nm, more preferably 2-20 nm. When the particle size is less
than 1 nm, it is difficult to produce the composite oxide. While, when the particle
size exceeds 30 nm, the particles easily cause the sintering and hence the surface
area of the particles becomes small and the contact area with the exhaust gas becomes
small and there is a problem that the activity is weak. Further, there is feared that
the pressure loss in the pass of the exhaust gas becomes large.
[0096] Onto the filter unit F1 showing a state that the surface of the filter unit F1 is
apparently coated with the alumina film (carrying film) 17 by independently covering
each surface of the SiC particles 16 with the alumina film 17 is carried a noble metal
or an element selected from elements of Group VIa and VIII in the Periodic Table as
a catalyst. As such an element are concretely mentioned platinum (Pt), palladium (Pd),
rhodium (Rh), nickel (Ni), cobalt (Co), molybdenum (Mo), tungsten (W), cerium (Ce),
copper (Cu), vanadium (V), iron (Fe), gold (Au), silver (Ag) and the like.
[0097] As the catalyst, therefore, at least one element selected from Pt, Au, Ag and Cu
as a noble metal, Mo, W as an element of Group VIa, Fe, Co, Pd, Rh, Ni as an element
of Group VIII and V, Ce as an element other the above in the Periodic Table or a compound
thereof may be carried on the alumina film 17.
[0098] For example, a binary alloy or a ternary alloy based on a combination of the above
elements is used as the compound. It is advantageous to use such an alloy together
with the rare earth oxide such as ceria, lanthana or the like acting as a co-catalyst
as mentioned above. The thus formed filter unit F1 is less in the deterioration due
to poisoning (lead poisoning, phosphorus poisoning, sulfur poisoning) and small in
the thermal deterioration and excellent in the durability. Moreover, compounds based
on a combination with the other element (oxide, nitride or carbide) may be used in
addition to the alloy of the above combination.
[0099] Incidentally, the binary alloy includes Pt/Pd, Pt/Rh, Pt/Ni, Pt/Co, Pt/Mo, Pt/W,
Pt/Ce, Pt/Cu, Pt/V, Pt/Fe, Pt/Au, Pt/Ag, Pd/Rh, Pd/Ni, Pd/Co, Pd/Mo/ Pd/W, Pd/Ce,
Pd/Cu, Pd/V, Pd/Fe, Pd/Au, Pd/Ag, Rh/Ni, Rh/Co, Rh/Mo, Rh/W, Rh/Ce, Rh/Cu, Rh/V, Rh/Fe,
Rh/Au, Rh/Ag, Ni/Co, Ni/Mo, Ni/W, Ni/Ce, Ni/Cu, Ni/V, Ni/Fe, Ni/Au, Ni/Ag, Co/Mo,
Co/W, Co/Ce, Co/Cu, Co/V, Co/Fe, Co/Au, Co/Ag, Mo/W, Mo/Ce, Mo/Cu, Mo/V, Mo/Fe, Mo/Au,
Mo/Ag, W/Ce, W/Cu, W/V, W/Fe, W/Au, W/Ag, Ce/Cu, Ce/V, Ce/Fe, Ce/Au, Ce/Ag, Cu/V,
Cu/Fe, Cu/Au, Cu/Ag, V/Fe, V/Au, V/Ag, Fe/Au, Fe/Ag, Au/Ag.
[0100] As an example of the ternary alloy, there are Pt/Pd/Rh, Pt/Pd/Ni, Pt/Pd/Co, Pt/Pd/Mo,
Pt/Pd/W, Pt/Pd/Ce, Pt/Pd/Cu, Pt/Pd/V, Pt/Pd/Fe, Pt/Pd/Au, Pt/Pd/Ag, Pt/Rh/Ni, Pt/Rh/Co,
Pt/Rh/Mo, Pt/Rh/W, Pt/Rh/Ce, Pt/Rh/Cu, Pt/Rh/V, Pt/Rh/Fe, Pt/Rh/Au, Pt/Rh/Ag, Pt/Ni/Co,
Pt/Ni/Mo, Pt/Ni/W, Pt/Ni/Ce, Pt/Ni/Cu, Pt/Ni/V, Pt/Ni/Fe, Pt/Ni/Au, Pt/Ni/Ag, Pt/Co/Mo,
Pt/Co, W, Pt/Co/Ce, Pt/Co/Cu, Pt/Co/V, Pt/Co/Fe, Pt/Co/Au, Pt/Co/Ag, Pt/Mo/W, Pt/Mo/Ce/
Pt/Mo/Ce, Pt/Mo/Cu, Pt/Mo/V, Pt/Mo/Fe, Pt/Mo/Au, Pt/Mo/Ag, Pt/W/Ce, Pt/W/Cu, Pt/W/V,
Pt/W/Fe, Pt/W/Au, Pt/W/Ag, Pt/Ce/Cu, Pt/Ce/V, Pt/Ce/Fe, Pt/Ce/Au, Pt/Ce/Ag, Pt/Cu/V,
Pt/Cu/Fe, Pt/Cu/Au, Pt/Cu/Ag, Pt/V/Fe, Pt/V/Au, Pt/V/Ag, Pt/Fe/Au, Pt/Fe/Ag, Pt/Au/Ag.
[0101] In order to carry these catalysts on the alumina film 17, there are considered various
methods. As a method suitable for this embodiment, an impregnation method, an evaporation
drying method, an equilibrium adsorption method, incipient wetness method or a spraying
method is advantageously applicable. Among them, the incipient wetness method is advantageous.
This method is a method wherein an aqueous solution containing a given amount of the
catalyst is added dropwise to the filter unit F1 and the impregnation of the catalyst
into pores of the filter unit F1 is stopped at a time of uniformly and slightly wetting
the surface of the carrier (incipient state) and thereafter the drying and firing
are conducted. That is, the dropwise addition of the catalyst-containing solution
on the surface of the filter unit F1 is carried out by using a bullet or an injection
syringe. The carrying amount of catalyst can be controlled by adjusting the concentration
of the solution.
[0102] Then, the method of carrying the catalyst on the filter unit F1 is explained, but
it is not limited to the following method.
[0103] A feature of the method of carrying the catalyst on the filter unit F1 in this embodiment
lies in that the alumina film 17 containing the rare earth oxide is formed on the
irregular surface of the filter unit F1 by a sol-gel process. Particularly, the alumina
film 17 containing the rare earth oxide is coated onto each surface of SiC particles
forming the cell wall 13 through the impregnation of the solution. Then, the alumina
film 17 is changed into an alumina film (carrier film) 17 showing a hair implant structure
that ceria-dispersed alumina stands up in form of small fibers at a microscopic section
through a step of treated with hot water after the calcining, and then a given amount
of the catalyst is adsorbed and fixed onto the surface of the alumina film 17.
[0104] Each step of (1) formation of alumina film 17 and (2) carrying of catalyst will be
described below.
(1) Coating of alumina film 17 onto filter unit F1
a. Preliminary treating step
[0105] In this step, oxidation is carried out by heating at 800-1600°C for 5-100 hours in
order to feed a required amount of Si promoting a chemical bonding with alumina on
each surface of SiC particles 16. If sufficient oxide film is existent on the surface
of SiC particles 16, this step may be naturally omitted. For example, SiC sintered
body itself contains about 0.8 mass% of SiO
2. When SiO
2 is increased for further improving the heat resistance, it is desirable to heat at
800-1600°C in an oxidizing atmosphere for 5-100 hours. When the temperature is lower
than 800°C, the oxidation reaction hardly occurs, while when it exceeds 1600°C, the
oxidation reaction extremely proceeds and the lowering of the strength in the filter
is caused. A recommendable condition is 1000-1500°C and 5-20 hours. In this condition,
SiO
2 enough to feed Si can be formed on the surface, and also the porosity and pore size
in the filter unit F1 are not changed and the pressure loss property is not damaged.
b. Solution impregnation step
[0106] In this step, a treatment coating the rare earth oxide containing alumina film 17
is carried out by impregnating each surface of the SiC particles 16 constituting the
cell wall 13 with a solution of a metal compound containing aluminum and rare earth
element, e.g. a mixed aqueous solution of aluminum nitrate and cerium nitrate or the
like through a sol-gel process.
[0107] As to aluminum-containing compound solution in the above mixed aqueous solution,
as a starting metal compound are used a metal inorganic compound and a metal organic
compound. As the metal inorganic compound are used Al(NO
3)
3, AlCl
3, AlOCl, AlPO
4, Al
2 (SO
4)
3, Al
2O
3, Al(OH)
3, Al and the like. Among them, Al(NO
3) and AlCl
3 are preferable because they are easily soluble in alcohol, water or the like and
are easy in the handling. As the metal organic compound are mentioned a metal alkoxide,
a metal acetylacetonate and a metal carboxylate. As a concrete example, there are
Al(OCH
3)
3, Al(OC
2H
3)
3, Al(iso-OC
3H
7)
3 and the like.
[0108] On the other hand, as the cerium-containing solution in the above mixed aqueous solution
are used Ce(NO
3)
3, CeCl
3, Ce
2(SO
4)
3, CeO
2, Ce(OH)
3, Ce
2(CO
3)
3 and the like.
[0109] As a solvent in the above mixed solution is used at least one selected from water,
alcohol, diol, polyvalent alcohol, ethylene glycol, ethylene oxide, triethanolamine,
xylene and the like.
[0110] In the preparation of the solution, hydrochloric acid, sulfuric acid, nitric acid,
acetic acid or fluoric acid may be added as a catalyst. Further, in order to improve
the heat resistance of the alumina film 17, at least one element selected from Ce,
Li, K, Ca, Sr, Ba, La, Pr, Nd, Si and Zr or a compound thereof other than oxide (nitrate,
chloride, sulfate, hydroxide or carbonate) may be added to the starting material in
addition to the rare earth oxide.
[0111] As an example of a preferable metal compound in this embodiment, mention may be made
of Al (NO
3)
3 and Ce(NO
3)
3. They are dissolved in the solvent at a relatively low temperature and is easy in
the preparation of the starting solution. Also, 1,3-butane diol is recommended as
a preferable solvent. A first reason of the recommendation lies in that the viscosity
is adequate and a gel film having a proper thickness may be formed on the SiC particles
16 at a gel state. A second reason is due to the fcat that this solvent forms a metal
alkoxide in the solution and a metal oxide polymer having oxygen-metal-oxygen bond
or a precursor of metal oxide gel may be easily formed.
[0112] The amount of Al(NO
3)
3 is desirable to be 10-50 mass%. When it is less than 10 mass%, the alumina amount
having a surface area for maintaining the activity of the catalyst for a long time
can not be carried, while when it exceeds 50 mass%, an amount of heat generation becomes
large in the dissolution and the gelation is easily caused.
[0113] Also, the amount of Ce(NO
3)3 is preferable to be 1-30 mass%. When it is less than 1 mass%, the oxidation of
the soot can not be promoted, while when it exceeds 30 mass%, the grain growth of
CeO
2 occurs after the firing.
[0114] The mixing ratio of Al(NO
3)
3 to Ce (NO
3)
3 is preferable to be 10:2. As Al(NO
3)
3 becomes richer, the dispersibility of CeO
2 particles after the firing can be improved.
[0115] In the preparation of the impregnating solution of the above metal compound, the
temperature is desirable to be 50-130°C. When the temperature is lower than 50°C,
the solubility of the solute is low, while when it exceeds 130°C, the reaction is
violently promoted to cause gelation and the use of the applying solution is impossible.
[0116] The stirring time is desirable to be 1-9 hours. When it is within the above range,
the viscosity of the solution is stable.
[0117] As to the above cerium-containing metal compound (Al(NO
3) and Ce(NO
3)
3), ZrO(NO
3)
2 or ZrO
2 is used as a zirconium source for producing a composite oxide with zirconium or a
solid solution in addition to the above example. In this case, it is preferable that
the above substance is dissolved in water or ethylene glycol to form a mixed solution
and dried and fired to form the above composite oxide.
[0118] In the above embodiment, it is important that the solution of the above metal compound
is sufficiently penetrated into all pores between SiC particles 16 in the cell wall
13. For this end, it is preferable to adopt a method wherein the filter unit F1 is
placed in a vessel and the solution of the metal compound is filled therein to conduct
deaeration, a method wherein the solution is flown into one side of the filter unit
F1 and deaeration is carried out at the other side, and the like. As the deaeration
apparatus may be used a vacuum pump or the like in addition to an aspirator. By using
such an apparatus can be removed air from the pores in the cell wall 13 and hence
the solution of the metal compound can be well fed onto the each surface of SiC particles
16.
c. Drying step
[0119] This step is a treatment that volatile components such as NO
2 and the like are removed by evaporation and the solution is gelated and fixed to
the surfaces of SiC particles 16 and at the same time extra solution is removed, which
is carried out by heating at 120-170°C for about 2 hours. When the heating temperature
is lower than 120°C, the volatile components hardly evaporate, while when it exceeds
170°C, the gelated film thickness become nonuniform.
d. Preliminary firing step
[0120] This step is a calcining treatment for removing residual components to form an amorphous
alumina film 17. Concretely, it is desirable to heat at a temperature of 300-500°C.
When the calcining temperature is lower than 300°C, the residual organic mass is hardly
removed, while when it exceeds 500°C, Al
2O
3 is crystallized and hence boehmite of small fibrous protrusion can not be formed.
e. Hot water treating step
[0121] This step is a treatment that the calcined filter unit F1 is immersed in hot water
for forming the alumina film 17 having a specified structure inherent to the above
embodiment. In this hot water treatment, the particles on the surface of the amorphous
alumina film 17 is immediately discharged into the solution at a sol state by a deflocculation
action and also boehmite particles produced by hydration are aggregated in form of
small fibrous protrusions and form a stable state against deflocculation.
[0122] That is, the rare earth oxide-containing alumina adhered to each surface of the SiC
particles 16 is stood up in form of small fibers (protrusions) by the hot water treatment,
which forms a rough surface indicating the hair implant structure. Therefore, there
is formed the alumina film 17 having a high specific surface area. In general, the
sintering of alumina mainly proceeds through surface diffusion, and when it is changed
into α-alumina phase, the specific surface area rapidly reduces. However, since silica
is enclosed in the alumina particles, it is considered that hole sites of alumina
are clogged with silica in the course of the heat treatment or silica moves toward
surfaces of needle-like particles to control the surface diffusion or the sintering
of the particles. Therefore, it is considered that the viscous flowing mechanism through
the sintering from the contact point between the needle-like particles is predominant
in the initial sintering stage of the filter unit F1, but silica shuts off the mass
transfer path between the needle-like particles at the last stage and hence the transfer
into α-alumina is obstructed and the sintering is not proceeded to maintain the high
specific surface area.
[0123] In the hot water treatment, the temperature is desirable to be 50-100°C. When it
is lower than 50°C, the hydration of the amorphous alumina film 17 does not proceed
and the boehmite of small fibrous protrusion is not formed. While, when it exceeds
100°C, water is evaporated and this step is hardly maintained over a long time. The
treating time is desirable to be not less than 1 hour. When it is less than 1 hour,
the hydration of the amorphous alumina is insufficient.
f. Firing step
[0124] In this step is conducted a treatment for dehydrating boehmite produced through hydration
to form alumina crystal. The firing temperature is preferable to be 500-1000°C. When
the temperature is lower than 500°C, the crystallization does not proceed, while when
it exceeds 1000°C, the sintering proceeds much and there is a tendency of lowering
the surface area.
(2) Carrying of catalyst
a. Solution preparing step
[0125] Onto the surface of the filter unit F1 is coated the rare earth oxide-containing
alumina film (carrying film) 17 having the hair implant structure as shown in FIG.
4(b) and a catalyst such as Pt or the like is carried on the irregular surface of
the alumina film 17. In this case, the carrying amount of the catalyst is determined
by adding dropwise and impregnating the aqueous solution containing Pt or the like
by a water absorbing amount of the filter unit F1 so as to slightly wet the surface
thereof.
[0126] For example, the water absorbing amount held by the filter unit F1 means that when
the measured value of the water absorbing amount of a dry carrier is 22.46 mass%,
if the carrier has a mass of 110 g and a volume of 0.1631, the carrier absorbs 24.79/l
of water. As a starting material of Pt is used, for example, a solution of dinitrodiamine
platinum nitrate ([Pt(NH
3)
2(NO
2)
2]HNO
3, Pt concentration: 4.53 mass%). In order to carry a given amount (1.7 g/l) of Pt,
it is sufficient to carry Pt of 1.7 (g/l)*0.163 (1) = 0.272 g on the carrier, so that
the solution of dinitrodiamine platinum nitrate (Pt concentration: 4.53%) is diluted
with a distilled water. That is, a weight ratio X (%) of solution of dinitrodiamine
platinum nitrate (Pt concentration: 4.53 mass%)/distilled water is 24.8 mass% as calculated
by X = 0.272 (Pt amount, g)/24.7 (water content, g)/4.53 (Pt concentration, mass%).
b. Solution impregnating step
[0127] The aqueous solution of dinitrodiamine platinum nitrate adjusted to a given amount
as mentioned above is added dropwise to both end faces of the filter unit F1 at constant
intervals through a pipette. For example, 40-80 droplets are added every one-side
face at constant intervals, whereby Pt is uniformly dispersed and fixed onto the surface
of the alumina thin film 3 covering the filter unit F1.
c. Drying, firing step
[0128] After the addition of the aqueous solution, the ceramic carrier is dried at 110°C
for about 2 hours to remove water content and transferred into a desiccator and left
to stand therein for 1 hour and thereafter the adhered amount is measured by an electron
weighing machine or the like. Then, the firing is carried out in N
2 atmosphere at about 500°C for about 1 hour to metallize Pt. The filter unit F1 is
used as a diesel particulate filter (hereinafter abbreviated as DPF simply). This
unit itself has only a function of catching particulates (floating particular substance:
PM) with the cell wall 13, but when the catalyst is carried thereon, hydrocarbon and
carbon monooxide in the exhaust gas can be oxdized.
[0129] Also, it is possible to conduct reduction of NOx even in an oxidizing atmosphere
as in the diesel exhaust gas when being carried with NOx selective reduction type
catalyst component or occlusion type catalyst component capable of reducing NOx. Moreover,
the particulates caught in DPF bring about the increase of pressure loss of DPF with
the deposition, so that it is usually necessary to remove them by burning treatment
or the like to regenerate DPF. The temperature starting the burning of soot (carbon),
which is a main component of the particulates included in the diesel exhaust gas,
is about 550-630°C. In this connection, when the catalyst is carried on DPF, the burning
reaction path of the soot is changed and energy barrier can be made low. Thus, the
burning temperature is largely lowered to 300-400°C and hence energy required for
regeneration can be reduced to constitute DPF system having a high regeneration efficiency
together with the action of ceria as mentioned above.
[0130] As mentioned above, it can be said that the filter unit F1 according to the embodiment
of the invention is preferable to apply to a system for particularly treating a diesel
exhaust gas, whereby the following functions can be expected:
- a. Function as an oxidation catalyst for diesel exhaust gas
- (1) Exhaust gas purifying function ... oxidation of THC (total hydrocarbon), CO
- (2) Function not obstructing operation of engine ... pressure loss
- b. Function as a diesel particulate filter provided with a catalyst
- (1) Exhaust gas purifying function ... burning temperature of soot, oxidation of THC,
CO
- (2) Function not obstructing operation of engine ... pressure loss
EXAMPLES
(Reference Example)
[0131]
- (1) 51.5% by weight of α-type silicon carbide powder and 22% by weight of β-type silicon
carbide powder are mixed at a wet state and added and mixed with 6.5% by weight of
an organic binder (methylcellulose) and 20% by weight of water. Then, the mixture
is added and mixed with small amounts of a plasticizer and a lubricant and extruded
to obtain a honeycomb green shaped body.
- (2) Then, the green shaped body is dried by using a microwave drying machine. Thereafter,
a part of through-holes 12 in the shaped body are sealed with a plug paste made of
a porous silicon carbide sintered body. Then, the plug paste is dried by again using
the drying machine. Subsequent to the end face sealing step, the dried shaped body
is degreased at 400°C and thereafter fired at 2200°C in an argon atmosphere under
an atmospheric pressure for about 3 hours. As a result, there is obtained a filter
unit F1 made of a porous silicon carbide sintered body.
- (3) A paste used for the formation of a sealing material layer 15 is prepared by mixing
23.3% by weight of ceramic fibers (alumina silicate ceramic fibers, shot content:
3%, fiber length: 0.1 mm - 100 mm), 30.2% by weight of silicon carbide powder having
an average particle size of 0.3 µm, 7% by weight of silica sol as an inorganic binder
(amount of the sol converted into SiO2 is 30%), 0.5% by weight of carboxymethyl cellulose as an organic binder and 39% by
weight of water and adjusting a viscosity of the mixture.
- (4) The, the paste for the formation of the adhesive layer is uniformly applied onto
each outer peripheral face of the filter units F1, while the outer peripheral faces
of the filter units F1 are closed to each other and dried and cured under conditions
of 50°C-100°C x 1 hour, whereby the filter units F1 are adhered to each other through
the sealing material layer 15. In this case, the thickness of the sealing material
layer 15 is set to 1.0 mm.
- (5) The filter units F1 are combined in 16 units in total of 4 units x 4 units to
finish a ceramic filter 9 of a square at section.
[0132] The thus obtained ceramic filter 9 is wound with a heat insulating material 10, and
then the ceramic filter 9 is placed in a casing 8 at this state, and a first exhaust
pipe 6, the casing 8 and a second exhaust pipe 7 are arranged in this order. Using
casings 8a-8d having four kinds of pipe arrangements as shown in FIG. 5 is fed an
exhaust gas from a diesel engine for a constant time. After the catching for 10 hours,
the ceramic filter 9 is taken out and cut to observe visually.
[0133] As a result, soot 16 is stored in the each kind of the casings 8a, 8b, 8c and 8d
as shown in FIG. 5. In case of the casing 8a, the first exhaust pipe 6 and the second
exhaust pipe 7 are arranged in a central portion of the casing 8 at section, so that
a greater part of the soot 16 is stored in the central portion of the ceramic filter
9. In case of the casing 8b, the first exhaust pipe 6 and the second exhaust pipe
7 are arranged on either one side of the peripheral edge portion of the casing 8,
so that a greater part of the soot 16 is stored on an elongated line of the exhaust
pipe toward the peripheral edge portion of the ceramic filter 9 at section. In case
of the casing 8c, the first exhaust pipe 6 is arranged in the central portion of the
casing 8 at section, while the second exhaust pipe 7 is arranged in the peripheral
edge portion of the casing 8 at section, so that a greater part of the soot is stored
in the central portion of the ceramic filter 9 and the peripheral edge portion arranging
the second exhaust pipe. In case of the casing 8d, the first exhaust pipe 6 is positioned
in an upper peripheral portion of the casing 8, while the second exhaust pipe 7 is
positioned in a lower peripheral portion of the casing 8 and is not opposed to the
first exhaust pipe 6, so that a greater part of the soot 16 is stored in portions
of the ceramic filter 9 corresponding to the arranged positions of the first exhaust
pipe 6 and the second exhaust pipe 7.
[0134] In the ceramic filter 9 is observed a tendency that the soot is largely stored in
the filter units F1 near to the downstream side end of the first exhaust pipe 6 and
the upstream side end of the second exhaust pipe 7.
[0135] It can be considered that the storing amount of the soot 16 is proportional to a
flowing amount of a gas. For example, the filter unit F1 positioned near to the downstream
side end of the first exhaust pipe is faster in the incoming gas rate as compared
with the filter unit F1 located far away therefrom (the amount is larger), and also
if the upstream side end of the second exhaust pipe is located opposite to the same
filter, the gas rate in the filter at this position more increases (the amount becomes
larger).
[0136] In the example mentioned later, therefore, the first exhaust pipe and the second
exhaust pipe are connected to the central portion of the casing as shown in FIG. 5(a).
In the ceramic filter 9, therefore, there can be another region producing the difference
of the flow rate between the central portion of 4 units and the peripheral portion
of 12 units. Next, comparative tests are carried out by applying various kinds of
filters to the two regions.
(Example 1)
[0137] In Example 1-1, the ceramic filter 9 is basically prepared in the same manner as
the reference example. In Example 1-1, however, a ceramic filter 9 of 16 filters in
total is prepared by using two kinds of SiC filter and cordierite filter as shown
in Table 1 and arranging 12 commercially available cordierite filters in the peripheral
portion and 4 SiC filters in the central portion. In this case, the thermal conductivity
of cordierite is 2 W/mk, and the thermal conductivity of SiC is 70 W/mk.
[0138] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8 at this state, and then the exhaust gas of the engine
is fed for a constant time as shown in the reference example. After the catching for
10 hours, the ceramic filter 9 is taken out and cut to conduct visual observation.
As a result, the storing amount at the peripheral portion becomes smaller than that
at the central portion as shown in FIG. 6(a).
[0139] Next, a new ceramic filter 9 is provided and the exhaust gas is fed thereto. After
the catching and regeneration are repeated 100 times, the ceramic filter 9 is taken
out to conduct the visual observation. As a result, no crack is observed in the filter
units F1. Also, the average regeneration ratio of the ceramic filter 9 is as high
as 95%, and no soot 16 is existent as visually observed after the cutting.
(Comparative Examples 1-1, 1-2)
[0140] Even in Comparative Examples 1-1, 1-2, the ceramic filter 9 is basically prepared
in the same manner as in the reference example. However, in Comparative Example 1-1,
a ceramic filter 9 is prepared by using 16 SiC filter units as shown in Table 1. In
Comparative Example 1-2, a ceramic filter 9 of 16 filters in total is prepared by
using two kinds of SiC filter and cordierite filter and arranging 4 cordierite filters
in the central portion and 12 SiC filters in the outer peripheral portion.
[0141] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8 at this state, and the exhaust gas of the engine is
fed for a constant time as shown in the reference example. After the catching for
10 hours, the ceramic filter 9 is taken out and cut to conduct visual observation.
As a result, in Comparative Examples 1-1 and 1-2, the storing amount in the peripheral
portion is made small likewise Example 1-1 as shown in FIG. 6(a).
[0142] Then, a new ceramic filter 9 is used and the exhaust gas is fed, and after the catching
and regeneration are repeated 100 times, the filter is taken out to conduct visual
observation. As a result, no crack of the filter unit F1 is observed in Comparative
Example 1-1. However, the average regeneration ratio of the ceramic filter is as low
as 85%, and as a result of visual observation on the cut face, a small amount of soot
is retained in the filter units F1 located at the outer peripheral portion after the
burning. In Comparative Example 1-2, cracks are observed in the filter units F1 located
at the central portion. Also, the average regeneration ratio is as low as 80%, and
as a result of visual observation on the cut face, a greater amount of soot is retained
in the filter units F1 located at the outer peripheral portion after the burning as
compared with Comparative Example 1-1.
[Table 1]
|
Example 1-1 |
Comparative Example 1-1 |
Comparative Example 1-2 |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Filter unit |
SiC |
Cordierite |
SiC |
SiC |
Cordierite |
SiC |
Cell Structure (mill/cell number) |
14/200 |
14/200 |
14/200 |
14/200 |
14/200 |
14/200 |
Porosity of filter |
42% |
42% |
42% |
42% |
42% |
42% |
Pore size of filter |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
Pressure loss (PMOg/L 13m/s) |
10 |
8 |
10 |
10 |
8 |
10 |
Average bending load |
350kgf/cm2 |
25kgf/cm2 |
350kgf/cm2 |
350kgf/cm2 |
25kgf/cm2 |
350kgf/cm2 |
Regeneration ratio |
95% |
85% |
80% |
(Example 2)
[0143] In this example, experiments are carried out as a typical example of ceramic filters
9 having different pressure losses. The ceramic filter 9 is basically prepared in
the same manner as in the reference example. In this case, the filters are prepared
by changing molds to adjust a thickness of cell wall 13 in the SiC filter unit or
cell number as shown in Table 2 and by changing a compounding ratio of starting materials
to adjust a porosity and a pore size as shown in Table 3.
[0144] With respect to the filter units F1, a standard pressure loss is measured (pressure
difference is measured when air of PMO g/L is flown at a flow rate of 13 m/s), and
the results are also shown in Tables 2 and 3.
[0145] Then, the ceramic filter 9 is prepared by setting 12 filters to the peripheral portion
and setting 4 filters to the central portion as shown in Table 4.
[0146] Next, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the filter
is taken out and cut to conduct visual observation. The results are also shown in
Table 4.
[0147] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, the ceramic filter 9 is taken
out to conduct visual observation. The results and regeneration ratio are shown in
Table 4.
[Table 2]
|
A |
Substrate B |
Substrate C |
Substrate D |
Substrate E |
Substrate F |
Substrate G |
Substrat eH |
① |
SiC |
SiC |
SiC |
SiC |
SiC |
SiC |
SiC |
SiC |
② |
12/200 |
14/200 |
16/200 |
16/200 |
12/70 |
12/200 |
12/300 |
12/400 |
③ |
42% |
42% |
42% |
42% |
42% |
42% |
42% |
42% |
④ |
10 |
10 |
10 |
10 |
10 |
10 |
10 |
10 |
⑤ |
9 |
10 |
13 |
14 |
8.9 |
8.9 |
9.1 |
9.1 |
⑥ |
11 |
12 |
15.6 |
16.8 |
15 |
13 |
10.3 |
9.5 |
① Filter unit
② Cell structure (mill/cell)
③ Porosity of filter (%)
④ Average pore size of filter (µm)
⑤ Pressure loss P 1 (PM 0 g / L, 13 m/ s)
⑥ Pressure loss P 2 (PM 5 g / L, 13 m/ s) |
[Table 3]
|
Substrate A |
Substrate I |
Substrate J |
Substrate K |
Substrate L |
Filter unit |
SiC |
SiC |
SiC |
SiC |
SiC |
Cell structure (mill/cell number) |
12/200 |
12/200 |
12/200 |
12/200 |
12/200 |
Average particle size of SiC(70 parts by weight) |
10 µm |
10 µm |
10 µm |
30 µm |
50 µm |
Average particle size of SiC(30 parts by weight) |
0.5 µm |
0.5 µm |
0.5 µm |
0.5 µm |
0.5 µm |
Shaping assistance (methyl cellulose) |
10 parts by weight |
6 parts by weight |
15 parts by weight |
10 parts by weight |
10 parts by weight |
Amount of organic pore forming material (acryl) |
0 parts by weight |
0 parts by weight |
5 parts by weight |
0 parts by weight |
0 parts by weight |
Average pore size of organic pore forming material (acryl) |
|
|
10 µm |
30 µm |
50 µm |
Porosity of filter unit(%) |
42% |
30% |
50% |
42% |
42% |
Average pore size of filter unit (µm) |
10 |
10 |
10 |
30 |
50 |
Pressure loss P1(PM0g/L 13m/s) |
9 |
12 |
8.5 |
8.6 |
8.3 |
[Table 4]
|
Central Portion |
Peripheral portion |
Pressure loss ratio (filer at peripheral portion /filter at central portion |
Deposited state of soot after the catching for 10 hours |
Catching and Regeneration of 100 times |
soot 0 g/ L |
soot 5 g/ L |
Average regeneration ratio |
Crack |
Example 2-1 |
Substrate A |
Substrate B |
1.1 |
|
Fig. 6(b) |
88% |
absence |
Example 2-2 |
Substrate A |
Substrate C |
1.4 |
|
Fig. 6(b) |
90% |
absence |
Example 2-3 |
Substrate A |
Substrate D |
1.6 |
|
Fig. 6(d) |
82% |
presence |
Comparative Example 2-1 |
Substrate A |
Substrate A |
1.0 |
|
Fig. 6(a) |
85% |
presence |
Example 2-4 |
Substrate H |
Substrate G |
|
1.1 |
Fig. 6(b) |
88% |
absence |
Example 2-5 |
Substrate H |
Substrate A |
|
1.2 |
Fig. 6(b) |
92% |
absence |
Example 2-6 |
Substrate H |
Substrate F |
|
1.4 |
Fig. 6(b) |
88% |
absence |
Example 2-7 |
Substrate H |
Substrate E |
|
1.6 |
Fig. 6(d) |
82% |
presence |
Comparative Example 2-2 |
Substrate H |
Substrate H |
|
1.0 |
Fig. 6(a) |
86% |
presence |
Example 2-8 |
Substrate A |
Substrate I |
1.3 |
|
Fig. 6(b) |
90% |
absence |
Comparative Example 2-3 |
Substrate A |
Substrate J |
0.9 |
|
Fig. 6(a) |
82% |
presence |
Example 2-9 |
Substrate K |
Substrate L |
1.04 |
|
Fig. 6(b) |
86% |
absence |
Example 2-10 |
Substrate A |
Substrate L |
1.1 |
|
Fig. 6(b) |
89% |
absence |
(Example 3)
[0148] Even in Example 3-1, the ceramic filter 9 is basically prepared in the same manner
as in the reference example. Two kinds of SiC filters having different strengths are
used in Example 3-1 as shown in Table 5. In order to change the strength, a higher
firing temperature is set to 2300°C - 3 hr, and a lower firing temperature is set
to 2100°C - 2 hr. The strength is measured by a three-point bending test described
in JIS R1625. In this case, a lower spun is set to 135 mm, and a head speed is set
to 0.5 mm/sec. This test is carried out 20 times, and the ceramic filter 9 is prepared
by selecting filters from the same production lot. In this case, the ceramic filter
9 is prepared by setting 12 SiC filters having an average bending load of 250 kg/cm
2 to the peripheral portion and 4 SiC filters having an average bending load of 350
kg/cm
2 to the central portion.
[0149] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the filter
is taken out and cut to conduct visual observation. As a result, the storing amount
in the peripheral portion of the filter becomes smaller than that in the central portion
as shown in FIG. 6(a).
[0150] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, the ceramic filter 9 is taken
out to conduct visual observation. As a result, no crack is observed in the filter
units F1. Also, the average regeneration ratio is as high as 90%, and the soot is
not existent as a result of visual observation on the cut face.
(Comparative Examples 3-1, 3-2)
[0151] Even in Comparative Examples 3-1, 3-2, the ceramic filter 9 is basically prepared
in the same manner as in the reference example. In Comparative Example 3-1, the ceramic
filter 9 is prepared by using 16 SiC filters having a standard average bending load
of 250 kg/cm
2 as shown in Table 5. In Comparative Example 3-2, the ceramic filter 9 is prepared
by using 4 SiC filter having an average bending load of 250 kg/cm
2 in the central portion and 12 SiC filters having a standard average bending load
of 350 kg/cm
2 in the peripheral portion.
[0152] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the filter
is taken out and cut to conduct visual observation. As a result, even in Comparative
Examples 3-1, 3-2, the storing amount in the peripheral portion becomes smaller than
that in the central portion as shown in FIG. 6 (a) .
[0153] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, the ceramic filter 9 is taken
out to conduct visual observation. As a result, cracks are observed in the filter
units F1 located at the central portion in Comparative Examples 3-1, 3-2.
[Table 5]
|
Example 3-1 |
Comparative Example 3-1 |
Comparative Example 3-2 |
Central portion |
Peripheral portion |
Central Portion |
Peripheral portion |
Central Portion |
Peripheral portion |
Filter unit |
SiC |
SiC |
SiC |
SiC |
SiC |
SiC |
Cell structure (mill/cell number) |
14/200 |
14/200 |
14/200 |
14/200 |
14/300 |
14/200 |
Porosity of filter |
42% |
42% |
42% |
42% |
42% |
42% |
Pore size of filter |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
Pressure loss (PMOg/L,13m/s) |
10 |
10 |
10 |
10 |
10 |
10 |
Average bending load |
350 kgf/cm2 |
250 kgf/cm2 |
250 kgf/cm2 |
250 kgf/cm2 |
250 kgf/cm2 |
350 kgf/cm2 |
Regeneration ratio |
90% |
85% |
88% |
(Example 4)
[0154] Then, the catching and regeneration are repeated by utilizing an engine having a
slow gas flow rate in the regeneration.
[0155] Example 4-1 is an example that a ceramic filter 9 is basically prepared in the same
manner as in Example 3. In Example 4-1, however, the ceramic filter 9 is prepared
by using two kinds of SiC filters having different strengths as shown in Table 6.
[0156] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the ceramic
filter 9 is taken out and cut to conduct visual observation. As a result, the storing
amount in the peripheral portion becomes smaller than that in the central portion
as shown in FIG. 6(a).
[0157] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, it is taken out to conduct
visual observation. In this case, the regeneration is conducted under a condition
of a slow flow rate as compared with the condition of Example 3. As a result, no crack
is observed in the filter units F1. Also, the average regeneration ratio is as low
as 80%. As a result of visual observation on the cut face, soot is existent.
(Comparative Examples 4-1, 4-2)
[0158] Even in Comparative Examples 4-1, 4-2, the ceramic filter 9 is basically prepared
in the same manner as in the reference example. In Comparative Example 4-1, the ceramic
filter 9 is prepared by using 16 SiC filters having a standard average bending load
of 250 kg/cm
2 as shown in Table 6. In Comparative Example 4-2, the ceramic filter 9 is prepared
by using 4 SiC filters having an average bending load of 250 kg/cm
2 in the central portion and 12 SiC filters having a standard average bending load
of 350 kg/cm
2 in the peripheral portion.
[0159] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the filter
is taken out and cut to conduct visual observation. As a result, even in Comparative
Examples 4-1, 4-2, the storing amount in the peripheral portion becomes smaller than
that in the central portion as shown in FIG. 6 (a) .
[0160] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, the ceramic filter 9 is taken
out to conduct visual observation. As a result, cracks are observed in the filter
units F1 located at the peripheral portion in Comparative Examples 4-1, 4-2.
[Table 6}
|
Example 4-1 |
Comparative Example 4-1 |
Comparative Example 4-2 |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Filter unit |
SiC |
SiC |
SiC |
SiC |
SiC |
SiC |
Cell structure (mill/cell number) |
14/300 |
14/200 |
14/200 |
14/200 |
14/200 |
14/200 |
Porosity of filter |
42% |
42% |
42% |
42% |
42% |
42% |
Pore size of filter |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
Pressure loss (PM0g/L,13m/s) |
10 |
10 |
10 |
10 |
10 |
10 |
Average bending load |
250 kgf/cm2 |
350 kgf/cm2 |
250 kgf/cm2 |
250 kgf/cm2 |
350 kgf/cm2 |
250 kgf/cm2 |
Regeneration ratio |
85% |
85% |
88% |
(Example 5)
[0161] Even in Example 5-1, the ceramic filter 9 is basically prepared in the same manner
as in the reference example. In Example 5-1, however, there are used two kinds of
SiC filter units F1 having different lengths as shown in Table 7. In this case, the
ceramic filter 9 is prepared by using 4 SiC filters having a standard length of 150
mm in the central portion and 12 SiC filters of 130 mm in the peripheral portion.
[0162] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the filter
is taken out and cut to conduct visual observation. As a result, soot is stored at
substantially the same positions in the central portion and the peripheral portion
of the filters as shown in FIG. 7(a).
[0163] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, the ceramic filter 9 is taken
out to conduct visual observation. As a result, no crack is observed in the filter
units F1. Also, the average regeneration ratio is as high as 90%. As a result of visual
observation on the cut face, soot is not existent.
(Comparative Examples 5-1, 5-2)
[0164] Even in Comparative Examples 5-1, 5-2, the ceramic filter 9 is basically prepared
in the same manner as in the reference example. In Comparative Example 5-1, however,
the ceramic filter 9 is prepared by using 16 SiC ceramic filters having a standard
length of 150 mm as shown in Table 7. In Comparative Example 5-2, the ceramic filter
9 is prepared by forming the peripheral portion with 12 SiC filters having a standard
length of 150 mm and forming the central portion with 4 SiC filters having a length
of 130 mm.
[0165] Then, the thus obtained ceramic filter 9 is wound with a heat insulating material
10 and received in a casing 8, and an exhaust gas of an engine is fed for a given
time as shown in the reference example. After the catching for 10 hours, the filter
is taken out and cut to conduct visual observation. As a result, in Comparative Example
5-1, the storing amount in the peripheral portion becomes smaller than that in the
central portion as shown in FIG. 6(a). In Comparative Example 5-2, the storing amount
in the peripheral portion is smaller than that in the central portion as shown in
FIG. 7(b), and the difference is large as compared with FIG. 6(a).
[0166] Thereafter, a new ceramic filter 9 is again provided and the exhaust gas is actually
fed. After the catching and regeneration of 100 times, the ceramic filter 9 is taken
out to conduct visual observation. As a result, no crack of the filter unit F1 is
observed in Comparative Example 5-1. However, the average regeneration ratio is as
low as 85%, and some soot retained after the burning is produced in the filter units
F1 at the peripheral portion as a result of visual observation on the cut face. Also,
in Comparative Example 5-2, crack is observed in the filter units F1 at the peripheral
portion. Further, the regeneration ratio is as low as 70% on average, and the amount
of soot larger than that of Comparative Example 5-1 after the burning is produced
in the filter units F1 at the peripheral portion as a result of visual observation
on the cut face.
[Table 7]
|
Example 5-1 |
Comparative Example 5-1 |
Comparative Example 5-2 |
|
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Filter unit |
SiC |
SiC |
SiC |
SiC |
SiC |
SiC |
Cell structure (mill/cell number) |
14/200 |
14/200 |
14/200 |
14/200 |
14/200 |
14/200 |
Porosity of filter |
42% |
42% |
42% |
42% |
42% |
42% |
Pore size of filter |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
10 µm |
Pressureloss (PM0g/L,13m/s) |
10 |
10 |
10 |
10 |
10 |
10 |
Average bending load |
350 kgf/cm2 |
350 kgf/cm2 |
350 kgf/cm2 |
350 kgf/cm2 |
350 kgf/cm2 |
350 kgf/cm2 |
total length |
150mm |
130mm |
150mm |
150mm |
130mm |
150mm |
regeneration ratio |
90% |
85% |
70% |
[0167] As seen from the above, according to the invention, there can be obtained the following
effects.
① In the filter of Example 1, the portion easily retaining soot and having a fast
flow rate can be rendered into a high temperature by changing the materials of two
or more kinds of filter units to produce a difference of thermal conduction. Therefore,
the uniform regeneration of the whole of the filter can be promoted.
② In the filter of Example 2, the flow of the exhaust gas is made easy flow toward
a filter having a low pressure loss by combining filter units having a high pressure
loss with filter units having a low pressure loss. Therefore, the uniform catching
and regeneration of the filter can be effectively carried out by arranging the filter
having a low pressure loss in a portion having a low exhaust gas flow amount. Also,
the uniform catching and regeneration as a whole of the filter can be carried out
when the pressure loss of the peripheral portion is 1.0-1.5 of the pressure loss of
the central portion.
③ In the filter of Example 2, the uniform catching and regeneration of the filter
can be effectively carried out by arranging the filters having a thin wall thickness
in the portion having a low exhaust gas flow amount and the filters having a thick
wall thickness in the portion having a high exhaust gas flow amount.
④ In the filter of Example 2, the uniform catching and regeneration of the filter
can be effectively carried out by arranging the filters having a high porosity in
the portion having a low exhaust gas flow amount and the filters having a low porosity
in the portion having a high exhaust gas flow amount.
⑤ In the filter of Example 2, the uniform catching and regeneration of the filter
can be effectively carried out by arranging the filters having a large pore size in
the portion having a low exhaust gas flow amount and the filters having a small pore
size in the portion having a high exhaust gas flow amount.
⑥ In the filter of Example 2, the uniform catching and regeneration of the filter
can be effectively carried out by arranging the filters having a high cell density
in the portion having a low exhaust gas flow amount and the filters having a low cell
density in the portion having a high exhaust gas flow amount.
⑦ In the filters of Examples 3 and 4, filters suitable for the catching amount can
be set by using filters having different strengths and arranging strong filters in
the portion easily subjected to thermal shock, so that the strength as a whole of
the filters is increased.
⑧ In the filter of Example 5, the aggregate is constructed by using filters having
a long length in the portion having a large fluid flow amount and filters having different
length in the portion having a small amount, whereby the catching amount of soot can
be made constant from a gas flowing section and the regeneration can be effectively
conducted.
[0168] When the pressure loss of the peripheral portion is 1.01-1.5 of the pressure loss
of the central portion, the catching and regeneration can be conducted more uniformly.
[0169] Moreover, the above embodiments of the invention can be modified as follows.
- a. Filter formed by arranging filters having a thick wall thickness and a low porosity
in the central portion of the filter aggregate and filters having a thin wall thickness
and a high porosity in the peripheral portion thereof.
- b. Filter formed by arranging filters having different lengths so as not to align
both end faces of an aggregate in the formation of the aggregate.
- c. Sectional shape of the filter aggregate is changed into a circle, an ellipsoid
or a triangle shape.
[0170] In the invention, a porous metal filter or a filter using ceramic fibers can be used
as a filter.
[0171] Furthermore, when the sectional shape of the filter is changed, only the plural filter
units having a shape other than a quadratic prism at cut section can be changed by
filters having a strength stronger than the other honeycomb filter having a quadratic
prism. Thus, the lacking of the strength in the filter of irregular shape is solved,
whereby the strength as the filter can be improved.
[0172] In the invention, the pore distribution can be made broad instead of sharp. In this
case, low pressure loss in the catching is obtained.
(Example 6)
[0173] This example is carried out for confirming the action and effect of the ceramic filters
using the above catalysts of different heat resistances. Each of the ceramic filters
produced under conditions shown in Table 8 (Example 6-1, Comparative Example 6-1 and
Comparative Example 6-2) is attached to an exhaust gas purifying apparatus of a diesel
automobile as a ceramic filter to conduct a purification test. For example, the catalyst
having a good heat resistance is used by including 10% of a rare earth oxide such
as CeC
2. Moreover, the distinction between the good and poor heat resistances in the catalyst
is judged by observing the change amount of specific surface area after the heat treatment
at 1200°C as shown in FIG. 9. In this test are examined the regeneration ratio of
the ceramic filter, temperature difference between the central portion and the peripheral
portion of the filter to be measured every each filter unit F1 in the ceramic filter
and the durability (regeneration ratio in the regeneration of 10 times). The results
are also shown in Table 8.
[0174] As shown in Table 8, each of the example and the comparative examples shows a high
value of not less than 90% at initial stage. The regeneration ratio after the use
of 10 times is apparently high in Comparative Example 6-1 having a heat resistance,
but the next value is Example 6-1 instead of Comparative Example 6-3. Also, as to
the regeneration temperature, Example 6-1 shows a low value of the temperature difference
as a whole as compared with the comparative examples. That is, the filter provided
with the catalyst having a high heat resistance is arranged in the portion having
a high regeneration temperature, so that the regeneration ratio is high after the
use of 10 times.
[Table 8]
Heat resistance |
Example 6-1 |
Comparative Example 6-1 |
Comparative Example 6-2 |
Comparative Example 6-3 |
Central Portion |
Peripheral portion |
Central Portion |
Peri pheral portion |
Central Portion |
Peripheral portion |
Central Portion |
Peripheral portion |
Heat resistance |
good |
standard |
good |
standard |
standard |
standard |
standard |
good |
Regeneration ratio |
92 % |
95 % |
90% |
93 % |
Regeneration ratio after use of several times |
78% |
80% |
50% |
60% |
Regeneration temperature |
650°C |
600°C |
650°C |
600°C |
650°C |
600°C |
650°C |
600°C |
(Example 7)
[0175] This example is carried out for confirming the action and effect of the ceramic filters
prepared by using filters carried with catalysts having different active temperatures.
That is, each of the ceramic filters produced under conditions shown in Table 9 (Example
7-1, Comparative Example 7-1, Comparative Example 7-2, Comparative Example 7-3) is
attached to an exhaust gas purifying apparatus of a diesel automobile to conduct the
purification test. Moreover, the distinction of the catalysts having different active
temperatures is judged by observing a relationship between regeneration temperature
and regeneration ratio as shown in FIG. 10. For example, a catalyst having a high-temperature
activity means that when an initial filter after the provision of the catalyst (low-temperature
active filter capable of well regenerating even at a low active temperature) is subjected
to a heat treatment at 800°C in an oxidizing atmosphere for 3 hours to lower the activity
of the catalyst, whereby the regeneration can not be sufficiently conducted unless
the active temperature is high. In this test are examined the regeneration ratio of
the ceramic filter (aggregate) and the temperature difference between the central
portion and the peripheral portion of the ceramic filter to be measured every each
filter unit F1. The results are shown in Table 9.
[0176] As shown in Table 9, the temperature of each ceramic filter (aggregate) is 650°C
in the central portion and 600°C in the peripheral portion. From this result, Example
7-1 and Comparative Example 7-1 show a high value of not less than 90% from an initial
stage. However, the ceramic filter of Comparative Example 7-3 in which the same ceramic
filters as in Example 7-1 are arranged in an opposite combination between the central
portion and the peripheral portion shows the regeneration ratio lower than that of
Example 7-1 because the activity in the peripheral portion is bad.
[Table 9]
Active temperature |
Example 7-1 |
Comparative Example 7-1 |
Comparative Example m7-2 |
Comparative Example 7-3 |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Central portion |
Peripheral portion |
Active temperature |
low |
high |
high |
high |
low |
low |
high |
low |
Regeneration ratio |
90% |
95% |
80% |
83% |
Regeneration ratio after use of several times |
70% |
75% |
65% |
70% |
Regeneration temperature |
650°C |
600°C |
650°C |
600°C |
650°C |
600°C |
650°C |
600°C |
(Example 8)
[0177] This example is carried out for confirming the action and effect of the ceramic filters
having different carrying amounts of the catalyst. That is, each of the ceramic filters
produced under conditions shown in Table 10 (Example 8-1, Example 8-2, Comparative
Example 8-1, Comparative Example 8-2, Comparative Example 8-3) is attached to an exhaust
gas purifying apparatus to conduct the purification test. In this test, the carrying
amount of the catalyst is determined as follows. At first, the ceramic filter is divided
into two regions of 4 filter units of the central portion and 12 filter units of the
peripheral portion. A ratio between the two regions is determined. Then, the carrying
amount in the filter is determined by equally dividing so as to satisfy the above
ratio every each filter. The regeneration ratio of the ceramic filter (aggregate),
the temperature difference between the central portion and the peripheral portion
of the filter to be measured every each filter unit and the durability (regeneration
ratio after the regeneration of several times) are examined. The results are shown
in Table 10.
[0178] As shown in Table 10, the temperature of each ceramic filter (aggregate) is 650°C
in the central portion and 600°C in the peripheral portion. At the initial stage,
the order of high regeneration ratio is Comparative Example 8-1, Example 8-1, Comparative
Example 8-3, Example 8-2 and Comparative Example 8-2 in this order. This result is
substantially the same order as the catalyst carrying amount in the ceramic filter
as a whole.
[0179] When Example 8-1 is compared with Comparative Example 8-3, the same amount of the
catalyst is carried on the ceramic filter (aggregate) itself, but the regeneration
ratio is higher in Example 8-1. Also, when Example 8-2 is compared with Comparative
Example 8-2, the same amount of the catalyst is carried on the ceramic filter (aggregate)
itself, but the regeneration ratio is higher in Example 8-2. From these results, it
is effective that the catalyst carrying amount is larger in the peripheral portion
than in the central portion.
[0180] Next, the results after the regeneration is repeated several times are considered.
As a result of comparison between Example 8-1 and Comparative Example 8-3 or between
Example 8-2 and Comparative Example 8-2, the regeneration ratio after the repetition
of several times tends to become high when the catalyst amount in the peripheral portion
is higher (Example 8-1, Example 8-2).

(Example 9)
[0181] This example is carried out for confirming the action and effect of the ceramic filters
(aggregates) having different carrying regions of the catalyst carrying amount. Each
of the ceramic filters produced under conditions shown in Table 11 (Example 9-1, Comparative
Example 9-1, Comparative Example 9-2, Comparative Example 9-3) is attached to an exhaust
gas purifying apparatus of a diesel automobile as a filter aggregate to conduct the
purification test.
[0182] In this test, the catalyst carrying amount is determined as follows. At first, the
ceramic filter (aggregate) is divided into two regions of 4 filter units of the central
portion and 12 filter units of the peripheral portion. A ratio between the two regions
is determined. Then, the carrying amount in the filter is determined by equally dividing
so as to satisfy the above ratio every each filter. The regeneration ratio of the
ceramic filter (aggregate), the temperature difference between the central portion
and the peripheral portion of the all filters to be measured every each filter unit
in the aggregate and the durability (regeneration ratio after the regeneration of
10 times) are examined. The results are shown in Table 11.
[0183] As shown in Table 11, the temperature of each ceramic filter (aggregate) is 650°C
in the central portion and 600°C in the peripheral portion. At the initial stage,
the order of high regeneration ratio is Example 9-1, Comparative Example 9-1, Comparative
Example 9-3 and Comparative Example 9-2 in this order. This result is substantially
the same order as the catalyst carrying amount in the ceramic filter as a whole.
[0184] The, as the regeneration ratio after the use of 10 times is measured, the regeneration
ratio in Example 9-1 is larger than in Comparative Example 9-3. Therefore, it is possible
to reduce the catalyst amount in the central portion being high temperature.
[Table 11]
Carrying region |
Example 9-1 |
Comparative Example 9-1 |
Comparative Example 9-2 |
Comparative Example 9-3 |
Central Peripheral portion |
Central Peripheral portion |
Central Peripheral portion |
Central Peripheral portion |
Carrying region from end face |
1/2 |
1 |
0 |
1 |
1/2 |
1/2 |
1 |
1/2 |
Regeneration ratio |
95% |
90% |
80% |
85% |
Regeneration ratio after use of several times |
65% |
58% |
60% |
63% |
Regeneration temperature |
650°C |
600°C |
650°C |
600°C |
650°C |
600°C |
650°C |
600°C |
[0185] As seen from the above explanation, according to the invention, there can be obtained
the following effects.
- (1) In the filter aggregate formed by combining a plurality of honeycomb filter units
carried with two or more catalysts having different heat resistances, the heat resistance
of the catalyst in the high-temperature portion is improved to prevent the sintering,
whereby the aggregate can be used over a long time without waste.
- (2) In the ceramic filter aggregate formed by combining filter units carried with
two or more catalysts having different catalyst active temperatures, it is possible
to improve the regeneration ratio in the low-temperature portion.
- (3) In the ceramic filter aggregate formed by combining filter units carried with
two or more catalysts of different carrying amounts, it is possible to improve the
regeneration ratio in the low-temperature portion.
- (4) In the ceramic filter formed by combining two or more kinds of filter units having
different carrying regions of the catalyst, it is possible to reduce the catalyst
amount of the filter in the high-temperature portion.
[0186] Moreover, the above embodiments of the invention may be changed as follows. That
is, heat is applied to the ceramic filter (aggregate) by the exhaust gas in these
embodiments, but the same exhaust gas purifying apparatus can be applied to the portion
of regenerating the filter by means of a heating means such as a heater or the like.
[0187] As shown in FIG. 13, a great amount of the catalyst may be adhered to the wall or
may be penetrated into the interior.
[0188] Next, the technical ideas grasped by the above embodiments are mentioned together
with their effects in addition to the technical idea described in the claims below.
- (1) The filter is not limited to only one kind. The ceramic filter capable of uniformly
catching by changing the pore size, porosity or the like is prepared by the aggregate
of filter units as described in the claims, whereby more uniform regeneration can
be conducted.
- (2) Although the catalyst is separately adhered every filter unit in the above embodiments,
the same filter as mentioned above can be prepared by partly adhering a seal onto
an end face of one filter and immersing into a slurry.
INDUSTRIAL APPLICABILITY
[0189] The ceramic filter according to the invention is excellent in the strength and is
excellent in the action of uniformly catching soot and uniformly conducting the regeneration,
so that it can be used in the exhaust gas purifying apparatus for an automobile. Particularly,
the invention can be utilized in an exhaust gas purifying apparatus of a diesel engine.